|Publication number||US1789507 A|
|Publication date||Jan 20, 1931|
|Filing date||Mar 13, 1929|
|Priority date||Mar 22, 1928|
|Publication number||US 1789507 A, US 1789507A, US-A-1789507, US1789507 A, US1789507A|
|Inventors||Godefridus Aarts Christianus J|
|Original Assignee||Godefridus Aarts Christianus J|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (8), Classifications (7)|
|External Links: USPTO, USPTO Assignment, Espacenet|
OHRISTLANUS J'OSEPHUS GODEFRIIDUS inseam-i PATENT OFFICE AARTS, OF VOORBUBG, NETHERLANDS PROCESS OF MAKING AN ADSORBENT COMPRISING CARBON, IRON, D IRON OXIDE g No Drawing. Application filed March 13, 1929, Serial No. 346,816, and in the etherlands Hatch 22, 1928.
This invention relates to the manufacture of a product having very strong adsorbent properties, consisting of a mixture of carbon iron and iron oxide.
The invention consists in conducting a gas containing 00 through and over finely divided iron oxide, at a temperature at which the iron oxide is'reduced"foralargepart but by no means entirely, and in which the mix-.
ture formed of iron and iron oxides serves as an oxygen-carrier, whereby one mol. CO is oxidized at the expense of another, so that, on the one hand, carbon is separated and CO is formed, and, on the other hand, the iron or iron oxide 'is alternatively oxidized and reduced, or reduced and oxldized, respectively, and therefore takes an active part in the reaction and as such is also present in the final product.
What occurs may probably be expressed as follows:
The first reaction, which occurs quickly and is not reversible, is
3Fezo3+ CO 2Fe304+ CO2 Then appears Fe O C023Fe0+ C0 (2) At a determined temperature, for example 375 0., this equilibrium will be possible gith a "determined relation between 00 and If the concentration of CO is too large, then the Fe O will be entirely reduced and 5 the reactionappears:
were reduced. The CO would then pass unchanged.
The following reactions, however, now appear:
' Fe+CO=C+FeO (4) and possibly 3Feo+oo=o+Fe;o;' (5) The reactions are practically not reversible-at the prevailing temperature, so that there are also obtained:
FeO-l-CO=Fe+CO (3) Fe+CO=FeO+C (4) that is, re-formation of FeO and re-appearance of (3).
The sum ofthese reactions is The result is, that with the continuous pas-j sage of CO over the iron and iron oxide, CO continues to be formed and a certain relation in the gas between CO and CO will appear, which is dependent on the reactionspeeds of Reactions (3) and (4).
If the content of CO is relatively high, then Reaction (2) and probably Reaction (5) can now appear also, the sum of-which again gives 2CO=CO +C, and thus a balance can be formed between all appearing reactions.
' The mixture of iron and iron oxide thus works apparently catalytically; but that there is no real catalysis here, appears from the fact that the conversion 2CO CO +C never occurs until the equilibrium of this reaction is attained but, even with the slowest gas stream, remains at a relation between CO and CO corresponding with the iron equilibrium at the prevailing temperature and pressure. 1
On the other, hand this equilibrium is already attained at considerable gas speeds and appears little dependent on the gas speed when there is sufiicient contact of the gases 90 with the finely divided contact mass. Practically 45435 per cent of CO can be obtained in the finished gases. also proves that there is no question here of a proper catalysis.
The temperature region in which the reaction occurs satisfactorily is fairly narrowly limit-ed between 350 and 450 C. and is of.
course also dependent on the CO and CO;
concentration in the gases used.
lVhere iron or iron oxide takes an essential part in the reaction, it is clear that the carbon formed is formed in very close connection with the iron, and further that the reaction proceeds more completely and more easily according as the iron oxide is more easily. and better accessible to the gas. 'Now the carbon formed itself renders the contact between the iron matter and .the gas more and more diflicult, and as the formation of carbon increases, the reaction becomes slower and more incomplete.
It has been found that there is no danger of poisoning the contact matter which, in other cases, namely with real catalysis, is always a source of great difiiculty in catalytic reactions.
Even unpurified generator gas can be used and no special attention need be paid to the purification of the gas for carrying out the processon a large scale. Also other gases containing CO can be used, such as water gas.
When a temperature satisfactory for the FeCO equilibrium can easily be maintained, the greatest difficulty is to provide a sufficient, even abundant, contact between the gas phase'and the contact matter consisting of iron and iron oxide. For this reason the contact mass is finely distributed over voluminous carriers containing carbon. By startin with such carriers no foreign matter is brought into the final product. By the separation of carbon the particles grow regularly and agglomerates are formed which can be pulverized for difierent purposes.
In this way a product can be obtained con taining about )ercent of carbon and in the finished gases a conversion of 6065 percent of the CO can be attained.
The presence of water vapor in the gas, however, is injurious, as then hydrocarbons are formed and the yield of carbon diminishes and the qualities ofthe product are not so good. The presence of hydrogen, on the other hand, is not appreciably injurious.
The contact matter required for the reaction can profitably be obtained by distributing an aqueous suspension of finely divided iron oxide or hydroxide over solid material containing carbon, such as charcoal, woodwool, hay or the like, and drying the suspension thereon. When the gases "are passed over such organic carriers, the latter are This regular content charred, but the fine distribution of the iron contact remains.
The following example illustrates the invention:
The reaction vessel is charged with wopdwool which has been soaked in an aqueous us ension of iron oxide. The strength of iliis suspension ma be chosen within very wide limits and depends somewhat on the nature of the wood-wool, which in its turn depends on the dimensions of the reaction vessel and must be of such a firmness that the charcoal skeleton formed therefrom is sufficiently strong in itself to remain standing in the vessel.
Preferably the quantity of wood-wool used is as small as practicable, in order that there may be as little charcoalas possible under the carbon separated by the reaction, An
iron oxide suspension of 20-40 per cent 8 strength has proved to be suitable in most cases.
The speed with which the gas may be led through the mass at the required temperature is particularly dependent on the dimensions of the vessel and is controlled in such a way that the duration of the contact of the gas *with'th'e" "filling"'material (wood-wool soaked in iron oxide) amounts to about 20 50 seconds (calculated for cold gas), and that this duration increases as the carbon separation proceeds. In this way acontent of about 60 per cent of CO (per cent of total volume of C0 CO can be obtained in the final gas.
For the industrial application it is desir-' able to conduct the reaction in a number of reaction vessels in series, so that the last vessel, charged with fresh wood-wool, 1s
traversed by spent hot gases, and thejjstih lation produ cts of the wood-p991 are dis- 1 c iargec with ese gases e ore the separation of active carbon begins. In this way the quality of the active carbon is not unfavourably influenced by the distillation products of the wood-wool.
The reaction can be continued in the above-- mentioned manner until the final product contains 80-90 per cent of carbon. From the mode of preparing the product, it follows that the latter mustbe a very intimate mixture of carbon, iron and iron oxide.
No success has attended efforts to separate the components by physical methods.
Separation by means of a magnet, whether a direct current magnet or an alternating current magnet, was not achieved; the only perceptible result was a general weakening of the magnetic permeability, without, however, any appreciable selective action.
Separation was also tried by means of a classifying apparatus through which an aqueous suspension of the product was slowly led. In this case the separation would be based on the great difference in specific gravity of the components. But in this case, also,
free from sulphur, phosphorus and other such not even a gradual purification was obtained. 1. A process of making a product possess- There was no considerable difference between ing very intense adsorbent properties and the purity of the first and of the last sample. consisting of a mixture of carbon iron and Furthermore it was tried in vain to effect iron oxide comprising the steps of distributa magnetic separation in an vaqueous suspenmg finely-divided iron oxide over a volumi- 7 sion. Also, in an alkaline suspension no renous carbonaceous carrier filling substansult was obtained. tially the entire reaction room and passing From the negative result of all these exa gas containing carbon monoxide through periments it appears that the product is a the carrier so treated at a temperature at very homogeneous and exceedingly finely diwhich the iron oxide is reduced for a large vided mixture, the separation of which into part but not exclusively. its components with the aid of mere physical 2. A process according to claim 1, in which means involves great difiiculties. This homothe gas containing carbon monoxide is pracgeneous and exceedingly fine division of the tically free from water vapour. contact matter in the product was found also 3. A process according to claim 1, in which in numerous incineration experiments. An the carrier comprises wood-wool and the iron explanation for this close connection of the oxide is distributed ereover m aqueous suscomponents follows from the reaction itself, pension and dried therewith. in which every molecule of carbon that is 4. Aprocess according to claim 1, in which formed requires immediate contact with an the iron oxide is distributed over the carrier iron molecule and is therefore amalgamated in aqueous suspension and dried therewith. with the latter in the most intimate way. 5. A process of making a product possess- Only by chemical methods a separation of ing very intense adsorbent properties and the components and preparation of a more consisting of a mixture of carbon, iron and or less pure carbon has been found possible. iron oxide, comprising the steps of distributi For most uses, however, it is not essential ing finely-divided iron oxide over a volumito separate the product and prepare pure nous carbonaceous carrier filling substancarbon from it; the mere mixture, just as it tially the entire reactionroom-yandpassing is obta-ined, ofli'ers practical advantages. a gas containing carbon monoxide through 'The chief application of the product is as the carrier so treated at a temperature bean adsorbent. It has the qualities of an actween 350-450 C.
we carbon and can be used for instance for 6. A process according to claim 5, in which the decolorizing of organic liquids, such as the finished gas contains 45-65% C0, of the sugar juices. For this use it is desirable to total volume of CO+CO= in the gases. produce the maximum carbon content. 7. A process according to claim 1, in which mo On the other hand, the iron content of the the gas containing carbon monoxide is passed product has the advantage that the whole over the carrier untilaphysically-inseparable mass can be separated magnetically, and the mixture of iron, iron oxide and carbon is filtration of the adsorbent from the solution obtained containing more than 80% of caris thereby made easier. bon.
The product can also be used as a, ig- CHRISTIANUS JOSEPHUS GODEFRIDUS AARTS. ment. After pulverizing, it constitutes a very ood black igi ngnt for the preparation of black ing, 1a ink, or the like.
A ffirther application of the product is as a carburizing agent. In some metallurgical processes it is desirable to restore to iron the carbon which has been oxidized during the refining operation, by means of acarbon,
1X6 deleterious components. Forms of the prodnot which are relatively rich in Fe lend themselves especially hereto, since the iron acts favourably by promoting the mixing.
The product also lends itself admirably to the making of electrodes for electric furnaces, since the iron content is variable and is homogeneously distributed through the mass. Thus a solid electrode with high conductive capacity is obtained.
Still another important use is as a filler v in the manufacture of rubber articles. In this case it shows properties similar to those of the carbon black now generally in use.
hat I claim is:
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US2479930 *||Aug 10, 1946||Aug 23, 1949||American Cyanamid Co||Recovery of precious metal values by cyanidation|
|US2601121 *||Apr 29, 1948||Jun 17, 1952||Standard Oil Dev Co||Preconditioning hydrocarbon synthesis catalyst and removing fines therefrom|
|US4008169 *||Mar 7, 1975||Feb 15, 1977||Mcgauley Patrick John||Preparation of iron oxide sorbent for sulfur oxides|
|US4260523 *||Jan 15, 1979||Apr 7, 1981||Siako Tsukamoto||Magnetized active carbon composition|
|US4607021 *||Jan 4, 1982||Aug 19, 1986||The Standard Oil Company||Activation of fly ash|
|US7879136 *||Feb 1, 2011||Engineering Performance Solutions, Llc||Magnetic activated carbon and the removal of contaminants from fluid streams|
|US20080226523 *||Mar 17, 2008||Sep 18, 2008||David W. Mazyck||Magnetic activated carbon and the removal of contaminants from fluid streams|
|US20130079223 *||Aug 24, 2011||Mar 28, 2013||Gwangju Institute Of Science And Technology||Method for preparing mesoporous carbon having iron oxide nanoparticles|
|U.S. Classification||502/404, 502/406, 502/417, 252/190|